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Патент USA US2403474

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Patented July 9, 1946
, 2,403,474
UNITED, STATES PATENT , OFFICE .
2,403,474 Y
ADDITIVE FOR LUBRICANTS
John D. Bartleson and Franklin Veatch, Cleve
land, Ohio, assignors to The Standard Oil Com
pany, Cleveland, Ohio, a corporation of Ohio
No Drawing. Application October 10, 1944,
-
Serial No. 558,079
17 Claims.
1
(Cl. 252—32.7)
2
This invention relates to lubricants and lubri
cant additives suitable for use under various
positions containing the combined sul?de, amine
conditions, including high temperatures or high
have discovered that this reaction results in good
pressures or both, as for example, use in an
and metal radicals or residues. In addition, we
yields and is free from the high losses inherent _
internal combustion engine operating at higher
temperatures and in which the lubricant is in
in processes forming sludges.
close contact with metallic surfaces, metal com
tions are suitable as addition agents for lubri
We. have also discovered that such composi
pounds and high temperature gases. Lubricat
cants and that when so employed they impart
ing oils, particularly when used under such con
markedly advantageous properties thereto.
ditions, are subject to breakdown with lacquer 10
The ?nal reaction product is readily made in ‘
deposition, sludge and acid formation, and tend
two steps, the ?rst of which is the reaction
to cause corrosion of the bearing and other metals ,
between the sul?de and the amine, and the sec
with which they are in contact.
ond of which involves the basic metal compound.
It is an object of the present invention to
The sul?de-amine reaction may be carried out
provide an agent which may be useful itself as
with direct admixture of the reactants, or by.
a lubricant, and which when added to lubricants
theiradmixture in the presence of a diluent which
will markedly inhibit the very objectionable depo
may or may not be subsequently removed. A
sition of lacquer, and, at the same time, inhibit
volatile inert solvent, such as one boiling in
acid and sludge formation, corrosion and other
the heptane-octane range, may be used as a
types of deterioration occurring under operating
diluent which is to be subsequently removed.
conditions.
Alternatively, a heavier oil such as white oil, or
A further object is the provision of lubricating‘
a lubricating oil of about the same properties
oils containing such an addition agent.
as that to which the new composition is to be
Another object of this invention is to provide
added, may be used as a diluent which is not to
heretofore unknown compositions made from raw 25 be removed. If a volatile solvent is used it may
materials not heretofore used in making prod
be selected so as to have a boiling point that
ucts of this type, together with processes for their
will assist in controlling the temperature if‘ the
production.
reaction is carried out under re?ux conditions.
Another object is to provide a novel composi
In a commercial embodiment of the invention a
tion which is superior in its functions to other 30 diluent probably would not be used unless it is
compositions now available and intended for this
a mineral oil, but this is not necessary.
same general purpose.
7
The sul?de-amine reaction may be carried out
Other objects'of this invention will be appar
at a temperature over a wide range. A tem
ent as it is more fully disclosed hereinafter.
perature in the range of about 100° to 400° F.,
In considering the chemistry involved in the 35 and preferably in the range of 250° to 400° F.
reactions pertinent to the’ invention, it is em
is preferred. The reaction is mildly exothermic
phasized at the outset that it is usually accepted
and on a commercial scale this heat developed
that one basic substance will not react with
may be used to maintain the temperature. The
another basic substance to give a reaction prod
ingredients may be added in increments if this
uct. It is also usually expected that when amines 40 is desirable for temperature control or other
-enter into reactions, the reaction products con
reasons.
,
taining the amine nitrogen tend to be basic
The ‘reaction is usually complete in four hours
in nature. Therefore, it would be expected that
or less time. The reaction time is a function of
the reaction product obtained from the reaction
the temperature, the amount of the‘ sul?de that
of an amine with a vsul?de of phosphorus, for
is to react, the subdivision of the sul?de, rate of
example, would not react at all with a basic metal
stirring, etc. The sul?de ,is insoluble in the
compound, such as sodium hydroxide; or if it
amine, reaction product, and diluent and the end
did react, that the amine reaction product would
point of the reaction is easily determined when
merely be decomposed by the stronger basic vcom
the
desired amount of the‘ sul?de is no longer
pound-and the amine liberated.
present as a solid in the reaction mixture.
Surprisingly enough, however, we have discov
The amine or amines may be reacted with the
ered that basic metal compounds do react with
sul?de or sul?des in mol ratios of one mol of
the reaction products obtained from the reac
amine to from 0.01 to 2.0 or more mols of sul?de.
tions of certain amines with a sul?de or sul?des
Even small amounts show a signi?cant improve
of phosphorus to give heretofore unknown com 55
ment. Economic factors may make it undesirable
2,408,474
4
I
~
-
3
to use more than about 2.0 mols of‘the sul?de.
Generally about 0.25 to 1.0 mol is the usual range 7
that will be used.
timony may be similarly employed.
A very large variety of amines have‘ been found
to react, for example, either aliphatic, aromatic
_
.,
7
product.
The pentasuliide is preferred though the ses-,
reason was used in the illustrative examples. Un
der suitable conditions sul?des of arsenic or an
-
longer present as a solid phase in the reaction .
' ~ It is bene?cial to have water present in the re
quisul?de or any other sul?de or mixtures of sul
?des may be employed. Phosphorus pentasulfide
is economic and readily available and'for this
.
uble in the sul?de-amine reaction product and
the amount that reacts is the amount that is no .
action and this may be introduced as water of
crystallization, or as a hydrate of the metal com
pound or it may be introduced separately.
A plurality of metals can be used such as sodi
10 um and calcium, calcium and barium, calcium
or zinc and aluminum or tin. If the amount of
the metal is small, the final product may be a
mixture of the initial reactionproduct and the
metal derivative. It is preferable, 'however, to
introduce a relatively large amount of the basic
The choice may be limited by the desired lubri 15 compound into the initial reaction product as
cant solubility characteristics of the ?nal metal
the desirable properties are attributed to the
derivative product. For this reason primary and
metal derivative.
‘
secondary aliphatic amines which have an all
The yield in this second reaction is also very
phatic radical of at least 12 carbon atoms are
barium
compound the
high. In the. case of the
preferred, and of these the (mono) or (di) octa 20 yield is from 90 to 95% and in the potassium
decyl or hexadecyl amines or mixtures contain
compound the yield is almost 100%.
or heterocyclic primary or secondary amines or
derivative primary or secondary amines thereof. ‘
ing at least one of them are given as illustrative.
After the reactants have all entered into so
Commercial dioctadecyl amine is the most readily
available of the amines and for this reason is used
in many of the illustrative examples.
‘
lution, the reaction is complete. The reaction
25 mass is then centrifuged or ?ltered to remove
water and any-traces of oil-insoluble by-product
The amine stock may be a mixture of different
amines of different molecular weight and degrees
of substitution. Tertiary amines, although not
as desirable may be present. Generally, the more
substances. If ‘an excess of the basic metal com
pound is used, the unreacted' excess may be sep
arated at this stage. If a volatile solvent was
used as a diluent, it may be removed by vacuum
30
saturated amines are preferred. _
distillation. The final products are usually waxy
solids at room temperatures, and clear, colored
The yield is very high and appreciable amounts
of oil insoluble or gaseous products are not formed.
An excess of any unreacted sul?de may be fil
tered off, but generally the amount is chosen so
that it will all react at the temperature selected,
and the reaction is continued until it is con
sumed.
_
'
The sul?de-amine reaction products may be
converted to their metal derivations by reaction
oils at temperatures above their melting points. "
These new compositions impart many desir
' able properties to lubricants to which they have
been added. They act as very powerful de
tergents therein, and as antioxidants and corro
sion inhibitors. They also improve the viscosity?
index and have a very striking effect as pour
point depressants. The metal derivatives are
with one or more metal compounds, such as their 40 far' superior to the correspondingv sul?de-amine
oxides or hydroxides. These metals may be one
reaction products as additives for lubricants.
or more of the following: an alkali metal, such
The amount of the above described metal de- '
as sodium, potassium and lithium; an alkaline
rivative of the sul?de-amine reaction product to
earth metal, such as calcium, barium, strontium;
be added to an oil or grease will depend upon the
or aluminum or other metal lower than alumi
characteristics of_ the oil or grease and the in-~
num in the electromotive series, such as zinc, lead,
tended use. Some oils have more of a tendency
chromium, cobalt, antimony, arsenic, ti , cop
to corrode metals, or to form acids, sludges and '
per, or molybdenum. The metal should be se
lacquer deposits than others, and such oils re
lected with reference to the use of the composi
quire larger quantities of, the addition agent.
50
tion and the properties desired in it. The alkali
Also’ oils that are intended for higher tempera
and alkaline earth metals have excellent deter
tures require larger amounts of the additive. In
gent characteristics. The heavier metals have
general, the range is from 1 to 10%, but under
surface corrosion inhibition characteristics. The
some circumstances amounts as low as 01%
preferred metals are group II and group III met
show a significant improvement. As to an up- I
55
als of the periodic table such as zinc, barium and
per limit, of course, itv may be uneconomical to
aluminum.
This second reaction may be carried out at
add more than is necessary to impart to the
lubricant the desired properties. Generally, not
temperatures in about the same range as de
over about 50% would usually be used.
scribed heretofore, a temperature of about-180?
The following examples of the preparation of
to 250° F. being preferred. This reaction is also 60 new compositions in accordance with the inven
usually completed in four hours or less time and
tion and tables of results of tests of lubricants
the same factors as to reaction time are involved
comprising ‘some of such compositions will serve
as discussed heretofore. A diluent may be used,
to illustrate and point out some advantagesbut
as described heretofore, but is‘ not necessary. If
in no wise to limit the scope of the invention as '
a diluent was used in the sulfide-amine reaction
otherwise disclosed and claimed herein.
it’may be carried over into this reaction step and
may be subsequently separated if desired.
’
From 7
about 0.25 to about 6.0 equivalents of the metal
compound may be used per mol of the sul?de in
the sul?de-amine reaction product, preferably
about 4.0 to about 6.0 equivalents in the case of
zinc or aluminum and also about 4.0 to 6.0 in the
case of barium. An equivalent is the quotient
of a mol divided by the valence of the metal con
"10
Example 1
(a) 200 grams of commercial dioctadecyl
amine (a mixture of about three parts of diocta
decylamine and one part of trioctadecylamine) ,
32 grams of phosphorus pentasulfide and 500
cubic centimeters of a heptane fraction of boil
ing range 90° to 100° C. were mixed and re?uxed
1.501‘ 48 hours. A homogeneous solution resulted.
cerned. The metalhydroxide is generally inso1-» 76
2,403,474
6
The heptane fraction was removed therefrom by
by centrifuging and then decanting the liquid.
distillation under reduced pressure and a waxy
residue was obtained. This analysed as 8.94%
sulfur and 6.55% phosphorus.
,
_
105 grams of product were obtained. It analysed
3.40% ash.
(b) The aluminum derivative was made from
_
(b) 80 grams of this waxy residue was heated
120 grams of oily product as obtained in Example
with 20 grams of barium hydroxide octahydrate
(Ba(OH>z.8HzO) for 4 hours at 190° F. and for
'1 hour at 250° F.; then the mixture was ?ltered
hot.
3a‘ and an aluminum gel freshly prepared by
treatment of 8.0 grams of AI(NO3)39H2O in aque
ous solution with excess ammonia and separation
of the gel. 108 grams of product were obtained.
The ?ltrate was a waxy brown solid at
room temperature. It analysed 1.60% phos
phorus, 3.79% sulfur and 3.69% barium.
10 It analysed 1.27% ash.
’
(c) The strontium derivative was made from
120 gramsof oily product as obtained in Example
311‘ and v8.5 grams of strontium hydroxide
Example 2
(a) 450 grams‘ of commercial dioctadecyl
Sr(OH)2.8H2O. 115 grams of product were ob~
amine, 71.9 grams of phosphorus pentasul?de 16 tained. It analysed 5.38% ash.
and 2250 cubic centimeters of a heptane fraction
(d) The lithium derivative was made from 120
’ of boiling range 90° to 100° C. were mixed and
grams of oily product as obtained in Example 3a,
re?uxed for 4 hours. A homogeneous solution
2.3 grams of LiOH and 2.0 grams of water. 110
resulted. The reaction yield was better than
grams of product were obtained.
'
95%.
,
.
.
20
-
(b) 102 grams of barium hydroxide Octahy
drate (Ba(OH) 2.81120) was added to the solution
and the whole re?uxed for 4 hours ‘more. Dur-'
ing this period some gas‘ was evolved from and
a small amount of white inorganic precipitatev 25
was formed in the mixture. The solution was
'
?ltered hot to remove water and insoluble by
products. The heptane fraction was removed by'
distillation under reduced pressure, mostly at
water bath temperatures and ?nally at 125° C. 30
, (e) The calcium derivative was made from 120
grams of oily product as obtained in Example 3a,
4.8 grams'of Ca(OH)2 and 1.2 grams of water.
115 grams of product were obtained. It analysed
0.90% ash.
,
'(f) The sodium derivative was made from 120
grams of oily product as obtained in Example 3a,
5.2 grams of NaOH and 2.4 grams of water. 115
grams of. product were obtained. It analysed
6.15% ash.
Example 6
The residue was a. clear red oil at 50° C. and a
waxy solid at room temperature. It analysed
Following the procedure of Example 4, the fol
18.4% ash, 12.45% barium, 2.83% sulfur and,
lowing derivatives containing different percent
ages of the metallic element (as shown by the
3.62% phosphorus. The reaction yield in this
35 diiferent ash analyses) were prepared from 500
step was 90 to 95%.
grams of product of Example 3a:
Example 3
(a) 15.2 grams- of potassium hydroxide and
10.0 grams of water gave 490 grams of product
(a) 1050 grams of commercial dio‘ctadecyl
amine, 267 grams of phosphorus pentasul?de and
3150 grams of #225 Red oil (an acid treated Mid
(95.3% yield) which analysed 2.71% ash.
40
Continent lubricating oil base stock) were mixed
and heated with agitation to 200° F. for 4 hours.
All the phosphorus pentasul?de had then re
acted. 4467 grams of a clear oily product were
obtained.
(b) 19.0 grams of potassium hydroxide and
12.5 grams of water gave 494 grams of product
(95.3% yield) which analysed 3.60% ash.
(c) 22.8 grams of potassium hydroxide and
15.0 grams of water gave 501 grams of product
(96.1% yield) which analysed 3.90% ash.
'
(b) 160 grams of this oily product and 13.6
Example 7
grams of barium hydroxide octahydrate were
(a)
59
grams
of
commercial dioctadecy-laminc.
mixed and heated with agitation to 200° F, for 4
19 grams of phosphorus pentasul?de and 177
hours. The reaction mixture was centrifuged hot
to remove water and oil insoluble by-products. 50 grams of white oil were mixed and heated with
vagitation for 4 hours at 300° F. The mixture was
154 grams of a waxy oil was obtained. This cor
?ltered hot. 222 grams of viscous brown oil were
responds to a 25% solution of the barium deriva
obtained.
tive of the amine-phosphorus pentasul?de reac
(1)) 80 grams of this brown oil and 20 grams of
tion product of the oil. ‘It analysed 5.80% ash,
barium hydroxide octahydrate were mixed and
525% barium, 1.49% sulfur and 1.61% phos
phorus.
,
heated with agitation for 4 hours at 200° F. and
then for 1 hour at 250° F. The mixture was ?l~
Example 4
tered hot. 90 grams of product were obtained.
((1)120 grams of oily product as obtained in
The overall reaction yield was better than 95%.
Example 3a, 5.4 grams of potassium hydroxide, 60 This product was a ?uid oil at 200° F‘. and a waxy
and 1.7 grams of water were processed according
solid at room temperature. It analysed 1.48%
to the procedure of Example 3b. 104 grams of
sulfur and 0.27% phosphorus.
~
product were obtained. It analysed 3.43% ash,_
Example 8
1.76% phosphorus and 1.48% sulfur.
Example 5
Following the procedure of Example 4 the cor
responding derivatives of the following metals
65
(a) 78 grams of commercial mono-octadecyl
amine-mono-hexadecylamine mixture, 33 grams
of phosphorus pentasul?de, and 500 cubic cen
timeters of a heptane fraction of boiling range
90° to 100° C. were mixed and re?uxed for 4
(a) The stannous tin derivative was made from 70 hours.
120 grams of oily product as obtained in Example
(b) Then 25.3 grams of potassium hydroxide
3a and a moist white precipitate of stannous
and 8.0 grams of water were added and the new_
hydroxide prepared from 7.2 grams of SnC12.2H2O
mixture re?uxed for 4 hours. The mixture was
by treatment in aqueous solution with excess sodi
then ?ltered hot and the ?ltrate heated with
um carbonate and separation of the precipitate 75 agitation to 250° F. to remove the heptane frac
were prepared: '
‘ ' 3,403,474
mately that of the piston ring'zone of a test
engine in operation. The rate of air?ow per
volume of oil is adjusted to the same as the
average for a test engine in operation. Cataly
tion diluent and leave the product as a residue.
110 grams of a brown waxy solid product were
obtained.
Example 9
(a) 525 grams. of commercial dioctadecyla
mine, 133.5 grams of phosphorus pentasulfide and
1575 grams of #225 Red' oil were mixed and
heated to 300° F. with agitation for 4 hours.
(b) 500 grams of the product resulting from
9a was mixed with 33 grams of zinc oxide and
heated to 200° F. with agitation for 1 hour; then
18 grams of water were added and the treatment
tic e?ects due to iron are empirically duplicated
by the addition of a soluble iron salt and those
due to lead-bromide by its addition. The dura
' ,tion of the test is adjusted to that usually used
in engine type tests. As is shown by the data
10 in the papers referred to, the laboratory‘tests
have been correlated with engine tests and the
properties of the oil in an engine may be deter
mined from the result of the laboratory tests.
The results'given in ‘the following tables‘were
continued for 2 hours more. The mass was heated
to 250° F. and blown with air for 2 hours, then it 16 obtained from tests using:
composition
not were obtained. It was an amber waxy ‘solid
at room temperature and analysed 3.82% ash;
In order to demonstrate the properties of the
metal derivatives of the phosphorus sul?de 20
amine reaction products in improving the char- ;
acteristics of lubricating oils and to compare such
derivatives in accordance with the invention with
phosphorus sul?de-amine reaction products and
with each other, a large number. of representa
tive additives were incorporated into conventional
lubricating oils. The lubricating oils contain
'
A 160 cubic centimeter sample of the lubricant
was centrifuged and filtered. 467 grams ofhprod
'70 liters of air per hour
100 square centimeters of steel surface
4.4 square centimeters of_copper-lead surface
1.0 square centimeter of copper surface
0.10% by weight of lead bromide powder
'
0.012% soluble iron calculated as FesOa (ferric
2-ethyl hexoate in C. P. benzene)
25
The “Standard” tests were run at 280° F. for 36
hours; the “Temperature tolerance”
(heavy
duty) tests were run at 350° F. for 10 hours. The
ing these additives were tested according to lab- '
lacquer is deposited on the steel tube and is de
oratory test procedures for evaluating the service
termined by difference in Weight of the tube after
stability of oils as described in a paper by R. E. 30 washing with chloroform and drying to constant
Burk, E. C. Hughes, W. E. Scovill and J. ,D.
weight. The oil insoluble sludge remaining in
the glass tube is thought to be related to similar
of the American Chemical Society in September,
sludge deposits in engines, and was rated visu
1941, and in another paper by the same authors
ally against color photographic standards, an
35
presented at the New York city meeting of the
appearance rating scale ranging from F (worst)
Bartleson presented at the Atlantic City meeting
American Chemical Society in September, .1944.
through A (best) being used. The corrosion was
The latter paper also correlates the results of
determined by difference in weight of the copper
and heavy metal pieces after scrubbing with
such laboratory tests with the so-called "Chevro
let engine test."
‘
The used oil was su?lcient to en
Essentially the laboratory test equipment con 40 chloroform.
able the determination of all of the usual oil
sists of a vertical, thermostatically heated, large
tests, viz. isopentane insolubles, viscosity, acid
glass test tube, into which is placed a piece of
number, etc.
'
steel tubing of about one third its length and
The data in the following three tables shows
of much smaller diameter. A piece of copper 45 the results obtained in testing our new additives
lead bearing strip is suspended within and from
by two tests described.
the upper end of the steel tube by a copper pin,
and an air inlet is provided for admitting air
.
“Standard” tests on a conventional Mid-Con
tinent acid treated lubricating oil base stock
into the lower end of the steel tube in such a
blended with Pennsylvania bright stock (5. A. E.
way that in rising the air will cause the oil 50 20), and compositions containing this oil and a
present to circulate. The test tube is ?lled with
an amount of the oil to be tested which is at least
su?‘icient to submerge the metals.
The ratios of surface active metals to the
volume of oil in an internal combustion test
metal derivative of a phosphorus pentasul?de
amine reaction product, were run on a number of
the additives; the results given in Table I are
representative:
'
Table I
Additive
o °-°°“
n n“'
from
adig?lilv‘gin
ExgImple per cent by
o.
weigh
Lacquer
Sludge‘
deposit
(in miili-
(isopentane
insoluble in
grams)
milligrams)
1°38 of“
cop r
Coppeb
Pe
‘
Acid
number
c
Viscosity
increase
>
Appear’
rggiclfg
lead
0
11. 4
1. 3
7. 4
2. 8
M2
3
1.8
0.6 i
1.2
0. 2
0. 9
11
A
3
3
3
3
1.0
1.3
5.8
1. 1
5.6
2.5
1.1
0. 0
0.8
0.4
0.6
0.9
3.0
0.0
1.1
3.4
0.4
1.7
1.9
2.7
8
27
27
18
A
A'
A.
A
3.0
0.9
13.0
v 0.0
0.4
0.4
10
3+
1.5
1. 5
2.8
0. 5
5.3
10. 3
1.2
0. 9
2.5
l. 8
1.1
1. 2
21
6
A
5+
engine are nearly quantitatively duplicated in the
test equipment. In the “Standard” test the tem
perature used is approximately the average tem- '
193. 3
Cir"grams
0s1°“) "7°
an int‘;
8
D+
The data in Table I show the marked improve
ment imparted to the oil composition in the im
portant‘lacquer deposit characteristic, as well as
in much decreased sludge formation, and strik
perature of the crankcase, and the “Temper
ature tolerance” test temperature is approxi- 75‘ ingly lower viscosity increase.
The detergent
2,403,474
10
properties of compositions containing the metal
derivatives of sulfide-amine reaction properties
silicate was found to prevent foaming upon bub
' bling of air through oil containing a few‘ per cent
are clearly pointed out in this table by the lower
lacquer deposit and better appearance ratings.
of the additive.
“Temperature tolerance” (heavyduty) tests on 5
compositions containing conventional Mid-Continent acid treated lubricating oil base stock
blended with Pennsylvania bright stock (8. A. E.
It,‘ will be obvious to one skilled in the art that
sul?de-amine reaction products and similar
products obtained by introducing phosphorus '
and/or sulfur into an amine as prepared accord
' ing to di?‘erent ‘procedures‘but having substan
20), and a phosphorus pentasul?deiamine reactially the same properties as those herein de
tion product, and a metallic element derivative 10 scribed, may be converted to metal derivatives in
of such a reaction product, were run‘ on the
barium derivative as illustrative; the results are
given in Table II.
,
Table II
Add-
C 090811 t'ra-
Y L
frolzgve dgftlil‘if-
81 d'
v U
accordance with the'invention. The invention as
claimed contemplates such compositions as set
forth in the followingclaims.
Ciliirrosion)
grams (in
W8 g
digit??? cap'énigne '1°SS°'_'
Exgrmple get 09:51:15‘, (in mill)i- ins?luble i1;
0.
~
grams
weight
in
,
‘0.0
4.8
3.0
3.0
1. s
Copper ‘(loggi
235.0
18.9
2.1
1. 9
1. o
1. 5
igrams
0.4
212.2
13.9
87.2
18.5
_
The data in Table 11 show the decidedly better '
eii'ects of the metal derivative as compared to the
sul?de-amine reaction product when used vas an
m?geg
.
2.2
0.1
1.1
0.5
-o. 2
0.6
'
viscosity Aggie
number increase
25.2
1.9
0.6
o. 1
‘
Acid
1,419
1.3
1.0
0.8
B+
131
71
69
so
1. 2
We claim:
B
13+
A
A
I
1. An additive for lubricants to improve their
additive for a lubricating oil. ‘This heavy duty 30 characteristics, comprising a metal derivative of
a reaction product of a sul?de of phosphorus and
test particularly accentuates detergent proper
an organic amine.
.
ties; the compositions with better detergent prop
2.
An
additive
for
lubricating
oils and greases
erties showing lower lacquer deposits and better
to improve their characteristics, comprising a
appearance ratings. It is clear from this table,
metal derivative of a reaction product of a sul
that the sul?de-amine reaction products are far ‘’ flde
of phosphorus and an organic amine having
inferior as additives to the corresponding metal
at least one hydrogen attached directly to the
derivatives as to this characteristic, as well as to
nitrogen.
sludge formation and effect on viscosity. The
3. An additive for lubricating oils and greases
data in this table also show a smaller amount‘of
40 to improve their characteristics, comprising a
the additive may be used to advantage.
group II metal derivative of a reaction product of
“Standard” tests and physical tests on heavy
phosphorus pentasul?cle and an amine having
duty lubricants containing a conventiona1 Mid
at least one hydrogen attached directly to the
Continent acid treated lubricating oil ‘base stock
nitrogen and having at least one radical of at
lended with Mid-Continent bright stock (S. A.
least twelve carbon atoms.
E.—2‘0 H. D. base), and a metal derivative of a
.
/
4. An additive for lubricating oils and greases
to improve their characteristics, comprising a
group III metal derivative of a' reaction product
of phosphorus pentasul?de and an organic amine
phosphorus pentasul?de amine reaction product
were run on the potassium and barium deriva
tives and the results are given in Table III.
Table III >
Concentra.
L
Corrosion
igrams (in
weig
acquor
Sludge
Additive from
883i‘); ‘grin
deposit
(isopentane
Example N 0.
V
pegg‘l-i‘ngtby
g
in milligrams
insoluble in
milligrams)
0. 0
3.0
4. 0
.
30. 4
0.9
0. 8
-
__
.
1°55 0‘
Copper
Ooppeb
lead
4. 6
1.0
3. 3
3. 0
1.4
3. 5
614. 8
1.0
0. 0
be
r
7. 0
1.2
_ l. 7
-
.
.
Viscosity Agnpgear Viscosity Pour
Solid
increase
‘
point
point
0- F.3O
a F. 25
—l0
—20
--l5
-25
tm mg
985
52
32
DAA
index
74. 2
79.7
76. 7
\
In addition to showing the qualities pointed out
in the discussion of the data in Tables I and II
the data in Table III show the marked improve
ment in pour point and solid point of this heavy
duty oil imparted thereto by- compositions of the
invention, as Well as improvement in viscosity
index.
.
'
In order to prevent foaming of the oil contain
ing a small proportion of the additive it is desir
able in some cases to add a very small amount of
tetra-amyl silicate, or an alkyl ortho carbonate,
ortho formate or ortho acetate.
0.0003% of
having at least one hydrogen attached directly to
p the nitrogen and having at least one aliphatic
’ radical of at least twelve carbon atoms.
'
5. An additive for lubricating oils and greases
to improve their characteristics, comprising a
metal derivative of a reaction product of phos
70 phorus pentasul?de and an octadecylamine hav
ing at least one hydrogen attached directly to the
nitrogen.
6. An additive for lubricating oils and greases
to improve their characteristics, comprising a
polyalkyl-silicone oil, or 0.001% of tetra-amyl 75 group II metal derivative of a reaction product
of phosphorus pentasul?de and an octadecyl
' ~2,403,434
.
11'
.
-
amine having at least one hydrogen attached
directly tothe nitrogen.’
‘
I
nitrogen and having at least one aliphatic radical
or at least twelve carbon atoms. containing from
about 4.0 to about 6.0 equivalents of barium per
,
7. An additive for lubricating oils and greases
to improve their characteristics,‘ comprising. a ‘
group III metal derivative of a reaction product
mol of- phosphorus pentasul?de residue.
- 14. An" additive forlubricating oils and greases
to ‘improve their characteristics, comprising an
of phosphorus pentasul?de and an octadecyl
aluminum derivative of a reaction product of
,amine having at least one hydrogen attached
phosphorus ‘pentasuliide and an organic amine
directly to the nitrogen.
' -' '4 I '
‘having at least one hydrogen attached directly to
8. An additive for ‘lubricating oils and greases, ' the nitrogen and having at ‘least one aliphatic
to improve their ‘characteristics, comprising‘ a
radical of at least twelve carbon atgms, contain
metal derivative of a reaction product of phos
ing vfrom about 4.0-’to" about‘ 6.0 equivalents of
phorus pentasul?de and an'amine having at least
aluminum per mol of phosphorus pentasul?de
one hydrogen attached directly-to the nitrogen
residue. '
_
>
and having at least one aliphatic radical of at
15. A lubricant comprising a mineral lubricat
l5,
"least twelve carbon atoms, reacted at a_ tem
ingoil and 0.01% to 50% of an addition agent
. perature in the range. of about 250° to about
comprising a zinc derivative of a reaction product
of - phosphorus pentasulflde and an octadecyl
400° F.
9. An additive for lubricating oilsand greases ‘ amine [having at least» one hydrogen attached
to improve their characteristics, comprising a 20 directly ,to the nitrogen reacted at a temperature
metal derivative of a reaction product of phos
in therange of about 250° to about 400° F., con
phoruspentaslil?de and an octadeqylaminehav
taining from‘ about 4.0 to about 6.0 equivalents of
ing at least onehydrogen attached directly to the‘
zinc per mol of phosphorus pentasul?de residue,
nitrogen, reacted in mol ratio ofone mol of the
and formed from the said sul?de-amine reaction
amine to from [0.25 to 1.0 mols of the sul?de.
product by reaction with a zinc'compound at a
10. An additive for lubricating oils. and greases 251 temperature in the range of about 180° to about
to improve their characteristics, comprising .a
250° F.
'
metal derivative of a reaction product of phos
16. A lubricant comprising a mineral lubricat
phorus pentasuliide, and an organic'amine hav
ing oil and from 0.01% to 50.0% of an addition
ing at least one hydrogen attached directly to the 80 agent comprising a barium derivative of a reac
nitrogen and having at least one aliphatic radical
tion product of phosphorus pentasul?de and an
of at least twelve carbon atoms, containing from
about 0.25 to 6.0 equivalents of the metal residue
octadecylamine having at least one hydrogen at
tached directly to the nitrogen, reacted at a tem
per mol of phosphorus pentasul?de residue.
perature in the range of about 250° to about 400°
' 11. An, additive for lubricating oils and greases
35 F., containing from about 4.0 to about 6.0 equiva
to improve their characteristics, comprising a
lentsof barium per mol of phosphorus pentasul
metal derivative of a reaction product of phos
?de residue, and formed from the said sul?de
phorus pentasul?deand an octadecylamine hav
amine reaction product by reaction with a barium
ing at least one hydrogen attached directly to the
compound at a temperature in the range of about‘
nitrogen‘, formed from the said sul?de-amine re 40 180° to about 250° F.
action ,product'by reaction with a compound of
17. A lubricant comprising a mineral lubricat- '
the said metal at a temperature in the range of
ing oil and 0.01% to 50.0% of an addition agent
about 180° to about 250° F.
comprising an aluminum derivative of a reaction
12.',An additive ,forflubncating oils and greases
product of phosphorus pentasuliide and an octa
to improve their characteristics, comprising a zinc 45 décylamine‘ having at, least one hydrogen at
‘derivative .of, areaction product of phosphorus
tached directly to the nitrogen reacted at a tem
pentasulfide and an'organic amine having at least
perature in the‘ range of about 250° to about 400°
one hydrogen a. tached directly to the nitrogen
F_‘., containingfromvabout 4.0 to about 6.0 equiva
andfhaving‘ atleast one aliphatic radical of at
lents of‘aluminum per mol of phosphorus penta
least twelve carbon atoms, containing from about 50 ‘tsiil?de residue, and formed from the said sul?de
4.0 to about 6.0' equivalents of zinc per mol ‘of
amine reaction product by__reaction with an alu
phosphoruspentasul?deresidue.
13. An additive for lubricating Oils ‘and’ greases _
to improve {their characteristics, comprising ,. a
minum compound at a temperature in the range
of about 180° to about-250° F.
barium derivativeof ‘a reaction-product of phos '55..
' phorus pentasul?de and an organic ,amine having
at least one hydrogen attached‘ directly to the ~
JOHN D. BARTLESON.
FRANKLIN VEATCH.
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